Born - Haber Cycles

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Edexcel International A Level Your notes

Chemistry
4.3 Energetics
Contents
4.3.1 Born-Haber Cycles - Key Terms
4.3.2 Born-Haber Cycles
4.3.3 Polarisation
4.3.4 Enthalpy of Solution - Key Terms
4.3.5 Enthalpy of Solution - Calculations
4.3.6 Enthalpy of Solution - Ionic Charge & Radius
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4.3.1 Born-Haber Cycles - Key Terms

Your notes
Born-Haber Cycles - Key Terms
Lattice energy
As with bond enthalpy, lattice energy (ΔlattHꝋ) can be expressed as a formation or dissociation process
As a formation process, it is the enthalpy change when 1 mole of an ionic compound is formed from its
gaseous ions (under standard conditions)
The ΔlattHꝋ is therefore exothermic, as when ions are combined to form an ionic solid lattice there is an
extremely large release of energy
Since this is an exothermic process, the enthalpy change will have a negative value
Because of the huge release in energy when the gaseous ions combine, the value will be a very
large negative value
The large negative value of ΔlattHꝋ suggests that the ionic compound is much more stable than its
gaseous ions
This is due to the strong electrostatic forces of attraction between the oppositely charged ions in
the solid lattice
Since there are no electrostatic forces of attraction between the ions in the gas phase, the
gaseous ions are less stable than the ions in the ionic lattice
The more exothermic the value is, the stronger the ionic bonds within the lattice are
The ΔlattHꝋ of an ionic compound cannot be determined directly by one single experiment
Multiple experimental values and an energy cycle are used to find the ΔlattHꝋ of ionic compounds
The lattice energy (ΔlattHꝋ) of an ionic compound can be written as an equation
For example, sodium chloride is an ionic compound formed from sodium (Na+) and chloride (Cl-)
ions
Since the lattice energy is the enthalpy change when 1 mole of sodium chloride is formed from
gaseous sodium and chloride ions, the equation for this process is:
Na+(g) + Cl-(g) → NaCl (s) ΔlattHꝋ = -776 kJ mol -1
Worked example
Writing equations for lattice energy
Write down the equations which represent the lattice energy of:
(i) Magnesium oxide
(ii) Lithium chloride
Answer
Answer 1:
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Mg2+ (g) + O2- (g) → MgO (s)

Answer 2: Your notes
Li+ (g) + Cl- (g) → LiCl (s)
Enthalpy change of atomisation
The standard enthalpy change of atomisation (ΔatHꝋ) is the enthalpy change when 1 mole of gaseous
atoms is formed from its element under standard conditions
The ΔatHꝋ is always endothermic as energy is always required to break any bonds between the atoms in
the element, to break the element into its gaseous atoms
Since this is always an endothermic process, the enthalpy change will always have a positive value
Equations can be written to show the standard enthalpy change of atomisation (ΔatHꝋ) for elements
For example, sodium in its elemental form is a solid
The standard enthalpy change of atomisation for sodium is the energy required to form 1 mole of
gaseous sodium atoms:
Na (s) → Na (g) ΔatHꝋ = +108 kJ mol -1
Worked example
Writing equations for the standard enthalpy change of atomisation
Write down the equations for the standard enthalpy change of atomisation (ΔatHꝋ) for:
(i) Potassium
(ii) Mercury
Answer
Answer 1:
Potassium in its elemental form is a solid, therefore the standard enthalpy change of atomisation is
the energy required to form 1 mole of K (g) from K (s)
K (s) → K (g)
Answer 2:
Mercury in its elemental form is a liquid, so the standard enthalpy change of atomisation of mercury
is the energy required to form 1 mole of Hg (g) from Hg (l)
Hg (l) → Hg (g)
Electron Affinity
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The electron affinity (ΔeaH) of an element is the energy change when one mole of electrons is gained
by one mole of gaseous atoms of an element to form one mole of gaseous ions under standard
conditions Your notes
For example, the first electron affinity of chlorine is:
Cl (g)+ e– → Cl- (g) ΔeaHꝋ = -364 kJ mol-1
The first electron affinity is always exothermic as energy is released when electrons are attracted to
the atoms
However, the second electron affinity of an element can be endothermic as illustrated by oxygen:
O– (g) + e– → O2- (g) ΔeaHꝋ = +844 kJ mol-1
This is because a large force of repulsion must be overcome between the negatively charged ion and
the second electron requiring a large input of energy
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4.3.2 Born-Haber Cycles

Your notes
Born-Haber Cycles - Construction
A Born-Haber cycle is a specific application of Hess’ Law for ionic compounds and enable us to
calculate lattice enthalpy which cannot be found by experiment
The basic principle of drawing the cycle is to construct a diagram in which energy increases going up
the diagram
The basic principle of a Born-Haber cycle

The cycle shows all the steps needed to turn atoms into gaseous ions and from gaseous ions into the
ionic lattice
The alternative route to the ionic lattice begins from the enthalpy of formation of the elements in their
standard states
Drawing the cycle for sodium chloride
A good starting point is to draw the elements with their state symbols about a third of the way up the
diagram
This is shown as the left hand side of the equation for the process indicated
The location is marked by drawing a horizontal bar or line which represents the starting energy level
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Your notes
Drawing a Born-Haber cycle step 1

Next, we need to create the gaseous ions
This is a two step process of first creating the gaseous atoms and then turning them into ions
Creating gaseous atoms is a bond breaking process, so arrows must be drawn upwards
It doesn't matter whether you start with sodium or chlorine
The enthalpy of atomisation of sodium is
Na (s) → Na (g) ΔatHꝋ = +108 kJ mol -1
The enthalpy of atomisation of chlorine is

½Cl2 (g) → Cl (g) ΔatHꝋ = +121 kJ mol -1
We can show the products of the process on the horizontal lines and the energy value against a vertical
arrow connecting the energy levels
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Your notes
Drawing a Born-Haber cycle step 2 - creating the gaseous atoms

Now the ions are created
The sodium ion loses an electron, so this energy change is the first ionisation energy for sodium
Na (g) → Na+ (g) + e– ΔieHꝋ = +500 kJ mol-1
The change is endothermic so the direction continues upwards

The chlorine atom gains an electron, so this is electron affinity
Cl (g) + e– → Cl- (g) ΔeaHꝋ = -364 kJ mol-1
The exothermic change means this is downwards

The change is displaced to the right to make the diagram easier to read
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Your notes
Drawing a Born-Haber cycle step 3 - creating the gaseous ions

The two remaining parts of the cycle can now be completed
The enthalpy of formation of sodium chloride is added at the bottom of the diagram
Na (s) + ½Cl2 (g) → NaCl (s) ΔfHꝋ = -411 kJ mol -1
This is an exothermic change for sodium chloride so the arrow points downwards
Enthalpy of formation can be exothermic or endothermic, so you may need to show it above the
elements ( and displaced to the right) for a endothermic change
The final change is lattice enthalpy, which is usually shown a formation. For sodium chloride the
equation is
Na+(g) + Cl-(g) → NaCl (s) ΔlattHꝋ
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Your notes
Drawing a Born-Haber cycle step 4 - completing the cycle

The cycle is now complete
The cycle is usually used to calculate the lattice enthalpy of an ionic solid, but can be used to find other
enthalpy changes if you are given the lattice enthalpy
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Worked example
Your notes
Constructing a Born-Haber cycle for KCl
Construct a Born-Haber Cycle which can be used to calculate the lattice energy of potassium chloride
Answer
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Your notes
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Worked example
Your notes
Constructing a Born-Haber cycle for MgO
Construct a Born-Haber Cycle which can be used to calculate the lattice energy of magnesium oxide
Answer
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Your notes
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Born-Haber Cycles - Calculations

Once a Born-Haber cycle has been constructed, it is possible to calculate the lattice energy (ΔHlattꝋ) by Your notes
applying Hess’s law and rearranging:
ΔfHꝋ = ΔatHꝋ + ΔatHꝋ + IE + EA + ΔlattHꝋ
If we simplify this into three terms, this makes the equation easier to see:
ΔHlattꝋ
ΔH f ꝋ
ΔH1ꝋ (the sum of all of the various enthalpy changes necessary to convert the elements in their
standard states to gaseous ions)
The simplified equation becomes
ΔfHꝋ = Δ1Hꝋ + ΔlattHꝋ
So, if we rearrange to calculate the lattice energy, the equation becomes

ΔlattHꝋ = ΔfHꝋ - Δ1Hꝋ
When calculating the ΔHlattꝋ, all other necessary values will be given in the question
A Born-Haber cycle could be used to calculate any stage in the cycle
For example, you could be given the lattice energy and asked to calculate the enthalpy change of
formation of the ionic compound
The principle would be exactly the same
Work out the direct and indirect route of the cycle (the stage that you are being asked to calculate
will always be the direct route)
Write out the equation in terms of enthalpy changes and rearrange if necessary to calculate the
required value
Remember: sometimes a value may need to be doubled or halved, depending on the ionic solid
involved
For example, with MgCl2 the value for the first electron affinity of chlorine would need to be
doubled in the calculation, because there are two moles of chlorine atoms
Therefore, you are adding 2 moles of electrons to 2 moles of chlorine atoms, to form 2 moles of Cl-
ions
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Worked example
Your notes
Calculating the lattice energy of KCl
Given the data below, calculate the ΔlattHꝋ of potassium chloride (KCl)
Answer
Step 1: The corresponding Born-Haber cycle is:
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Your notes
Step 2: Applying Hess’ law, the lattice energy of KCl is:

ΔlattHꝋ = ΔfHꝋ - [(ΔatHꝋ K) + (ΔatHꝋ Cl) + (IE1 K) + (EA1 Cl)]
Step 3: Substitute in the numbers:

ΔlattH = (-437) - [(+90) + (+122) + (+418) + (-349)] = -718 kJ mol-1
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Worked example
Your notes
Calculating the lattice energy of MgO
Given the data below, calculate the of ΔlattHꝋ magnesium oxide of magnesium oxide (MgO)
Answer
Step 1: The corresponding Born-Haber cycle is:
Page 17 of 32
Your notes
Step 2: Applying Hess’ law, the lattice energy of MgO is:

ΔlattHꝋ = ΔfHꝋ - [(ΔatHꝋ Mg) + (ΔatHꝋ O) + (IE1 Mg) + (IE2 Mg) + (EA1 O) + (EA2 O)]
Step 3: Substitute in the numbers:

ΔlattHꝋ = (-602) - [(+148) + (+248) + (+736) + (+1450) + (-142) + (+770)]
= -3812 kJ mol-1
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4.3.3 Polarisation
Your notes
Polarisation
Theoretical lattice energies assume a perfect ionic model where the ions are 100% spherical and the
attractions are purely electrostatic
So overall, there has a been a complete and irreversible exchange of outer shell electrons between
the two elements in the compound so that one ion is negatively charged and the other ion
positively charged and the charges are whole values
Theoretical lattice energy can differ from measured lattice energy
This is because covalent character is introduced when there is polarisation of the anions
When this occurs, the cation attracts electrons from the anion therefore distorting electron density of
the anion leading to a degree of covalent character
Polarisation of anion leading to covalent character

Cations
A cation with a large charge density will have a larger polarising power
The charge density can be calculated as the charge of the cation divided but the surface area, for
example
K+ will have a lower polarising power than Li+ as the ionic radius is greater
Na+ will have a lower polarising power than Mg2+ as the charge is smaller
So a cation that is small and highly charged will have the greatest polarising power
Anions
Anions are polarised
The polarisability of the anion depends of its ionic radius
The larger the ionic radius the more easily it will be distorted, for example
Br- will be more polarisable than Cl- as the ionic radius is larger
A rough approximation of the charge density can be determines by dividing the charge by the square
of its ionic radius and this can help us estimate the extent of covalent character
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charge
charge density ∼
r2 Your notes
Comparing the Covalent Character of NaCl and MgCl2
Page 20 of 32
4.3.4 Enthalpy of Solution - Key Terms

Your notes
Enthalpy of Solution - Key Terms
Enthalpy of solution
The standard enthalpy change of solution (ΔsolH) is the enthalpy change when 1 mole of an ionic
substance dissolves in sufficient water to form an infinitely dilute solution
The symbol (aq) is used to show that the solid is dissolved in sufficient water
For example, the enthalpy changes of solution for potassium chloride are described by the
following equations:
KCl (s) + aq → KCl (aq)
OR
KCl (s) + aq → K+ (aq) + Cl- (aq)
ΔsolHꝋcan be exothermic (negative) or endothermic (positive)
Enthalpy of hydration
The standard enthalpy change of hydration (ΔhydH) is the enthalpy change when 1 mole of a specified
gaseous ion dissolves in sufficient water to form an infinitely dilute solution
For example, the enthalpy change of hydration for magnesium ions is described by the following
equation:
Mg2+(g) + aq → Mg2+(aq)
Hydration enthalpies are the measure of the energy that is released when there is an attraction
formed between the ions and water molecules
Hydration enthalpies are exothermic
When an ionic solid dissolves in water, positive and negative ions are formed
Water is a polar molecule with a δ- oxygen (O) atom and δ+ hydrogen (H) atoms which will form ion-
dipole attractions with the ions present in the solution
The oxygen atom in water will be attracted to the positive ions and the hydrogen atoms will be
attracted to the negative ions
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Your notes
The polar water molecules will form ion-dipole bonds with the ions in solution causing the ions to
become hydrated
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4.3.5 Enthalpy of Solution - Calculations

Your notes
Enthalpy of Solution - Calculations
Questions in this topic typically ask you to calculate the hydration enthalpy of one of the ions, given the
lattice enthalpy, enthalpy of solution and hydration enthalpy of the other ion.
This can be done by constructing an appropriate energy cycle and using Hess's Law to find the
unknown energy value
The energy cycle above shows that there are two routes to go from the gaseous ions to the ions in an
aqueous solution:
Route 1: going from gaseous ions → ionic solid → ions in aqueous solution (this is the indirect
route)
Route 2: going from gaseous ions → ions in aqueous solution (this is the direct route)
According to Hess’s law, the enthalpy change for both routes is the same, such that:
ΔhydHꝋ = ΔlattHꝋ + ΔsolHꝋ
Each ion will have its own enthalpy change of hydration, ΔHhydꝋ, which will need to be taken into
account during calculations
The total ΔhydHꝋ is found by adding the ΔhydHꝋ values of both anions and cations together
Worked example
Constructing an energy cycle for KCl
Calculate the enthalpy of hydration of the chloride ion given the following data:
ΔlattHꝋ [KCl] = -711 kJ mol-1
ΔsolHꝋ [KCl] = +26 kJ mol-1
ΔhydHꝋ [K+] = -322 kJ mol-1
Answer
Step 1: Draw the energy cycle and make ΔhydH[Cl-] the subject of the formula:
Page 23 of 32
Your notes
Step 2: Substitute the values to find ΔhydH[Cl-]

ΔhydH[Cl-] = (-711) + (+26) - (-322) = -363 kJ mol-1
Alternative Diagram
You can also draw a Born-Haber cycle as an alternative approach to the same problem
Energy level diagram:
Page 24 of 32
Your notes
Page 25 of 32
Worked example
Your notes
Constructing an energy cycle and energy level diagram of MgCl2
Construct an energy cycle to calculate the ΔhydHꝋof magnesium ions in magnesium chloride, given the
following data:
ΔlattH [MgCl2] = -2592 kJ mol-1
ΔsolH [MgCl2] = -55 kJ mol-1
ΔhydH [Cl-] = -363 kJ mol-1
Answer
Step 1: Draw an energy cycle:
Step 2: Substitute the values to find ΔHhydꝋ [Mg2+]

ΔHhydꝋ[Mg2+] = (-2592) + (-55) - (2 x -363) = -1921 kJ mol-1
Page 26 of 32
Alternative route to find ΔhydHꝋ[Mg2+]

Here is the same solution using a Born-Haber cycle Your notes
Exam Tip
It doesn't matter whether you use Hess cycles or Born-Haber style cycles to solve these problems as
long as the information is correctly labelled and the direction of the arrows matches the
definitions.Exam problems in this topic often show diagrams with missing labels which you have to
complete and find unknown values.The key to success in energy cycle calculations is not to panic, but
have a careful step-by-step approach, show your workings and use brackets to separate
mathematical operations from the enthalpy changes.
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Enthalpy of Solution - Predictions

When an ionic compound dissolves in water, there are two changes that need to take place Your notes
The lattice structure needs to be broken down and the ions must become hydrated
The breaking down of the lattice structure is endothermic (equivalent to the reverse lattice energy) it
also results in an increased number of moles of particles present, therefore entropy will increase
The hydration of the ions is an exothermic process but results in water molecules becoming more
ordered as they arrange themselves around the cations and anions
This increasing in order decreases the entropy of the water
Therefore to explain why some ionic compounds are soluble and some are insoluble we must consider
both entropy and enthalpy changes involved
As we have seen previously
ΔStotal = Δ Ssystem+ Δ Ssurroundings
And since
∆ s ol H
Δ Ssurroundings = −
T
The expression can become
∆ s ol H
Δ Stotal= Δ Ssystem −
T
Therefore the solubility of an ionic solid depends upon three factors

The entropy of the system, ΔSsystem
The enthalpy change of solution, ΔsolH
The temperature, in K, of the water, T
If we consider ammonium nitrate, NH4NO3 (s), at 298 K
NH4NO3 (s) → NH4+ (aq) + NO3- (aq)
The enthalpy change of solution, ΔsolH = +25.8 kJ mol-1
The temperature, in K, of the water, T = 298 K
ΔSsystem = S[NH4+ (aq)] + S[NO3- (aq)] - S[NH4NO3 (s)]
= +113.4 + 146.4 - 151.1

= +108.7 J K-1 mol-1
∆ sol H
∆ S surrounding s = −
T
+ 25800
=−
298
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= -86.6 J K-1 mol-1

Therefore the total entropy is: Your notes
ΔStotal = Δ Ssystem+ Δ Ssurroundings
= +108.7 + (-86.6)
= +22.1 J K-1 mol-1
If the entropy change is positive, as it is for dissolving ammonium nitrate in water at 298 K, then this is
thermodynamically spontaneous
The activation energy (Ea) for this reaction is very low, we can conclude that at 298 K, ammonium nitrate
is soluble in water
Page 29 of 32
4.3.6 Enthalpy of Solution - Ionic Charge & Radius

Your notes
Enthalpy of Solution - Ionic Charge & Radius
Factors affecting lattice enthalpy
The two key factors which affect lattice energy, ΔHlattꝋ, are the charge and radius of the ions that make
up the crystalline lattice
Ionic radius
The lattice energy becomes less exothermic as the ionic radius of the ions increases
This is because the charge on the ions is more spread out over the ion when the ions are larger
The ions are also further apart from each other in the lattice
The attraction between ions is between the centres of the ions involved, so the bigger the ions the
bigger the distance between the centre of the ions
Therefore, the electrostatic forces of attraction between the oppositely charged ions in the lattice
are weaker
For example, the lattice energy of caesium fluoride (CsF) is less exothermic than the lattice energy of
potassium fluoride (KF)
Since both compounds contain a fluoride (F-) ion, the difference in lattice energy must be due to
the caesium (Cs+) ion in CsF and potassium (K+) ion in KF
Potassium is a Group 1 and Period 4 element
Caesium is a Group 1 and Period 6 element
This means that the Cs+ ion is larger than the K+ ion
There are weaker electrostatic forces of attraction between the Cs+ and F- ions compared to K+
and F- ions
As a result, the lattice energy of CsF is less exothermic than that of KF
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Your notes
The lattice energies get less exothermic as the ionic radius of the ions increases
Ionic charge
The lattice energy gets more exothermic as the ionic charge of the ions increases
The greater the ionic charge, the higher the charge density
This results in stronger electrostatic attraction between the oppositely charged ions in the lattice
As a result, the lattice energy is more exothermic
For example, the lattice energy of calcium oxide (CaO) is more exothermic than the lattice energy of
potassium chloride (KCl)
Calcium oxide is an ionic compound which consists of calcium (Ca2+) and oxide (O2-) ions
Potassium chloride is formed from potassium (K+) and chloride (Cl-) ions
The ions in calcium oxide have a greater ionic charge than the ions in potassium chloride
This means that the electrostatic forces of attraction are stronger between the Ca2+and O2-
compared to the forces between K+ and Cl-
Therefore, the lattice energy of calcium oxide is more exothermic, as more energy is released
upon its formation from its gaseous ions
Ca2+ and O2- are also smaller ions than K+ and Cl-, so this also adds to the value for the lattice
energy being more exothermic
Page 31 of 32
Factors affecting enthalpy of hydration

Hydration enthalpies are exothermic as energy is given out as water molecules bond to the metal ions Your notes
The negative ions are attracted to the δ+ hydrogens on the polar water molecules and the positive
ions are attracted to the δ- oxygen on the polar water molecules
The higher the charge density the greater the hydration enthalpy (e.g. smaller ions or ions with larger
charges) as the ions attract the water molecules more strongly, for example:
Fluoride ions, F-, have more negative hydration enthalpies than chloride ions, Cl-
Magnesium ions, Mg2+, have a more negative hydration enthalpy than barium ion, Ba2+
Page 32 of 32

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Edexcel International A Level Your notes

4.3.1 Born-Haber Cycles - Key Terms

Mg2+ (g) + O2- (g) → MgO (s)

4.3.2 Born-Haber Cycles

The basic principle of a Born-Haber cycle

Drawing a Born-Haber cycle step 1

The enthalpy of atomisation of chlorine is

Drawing a Born-Haber cycle step 2 - creating the gaseous atoms

The change is endothermic so the direction continues upwards

The exothermic change means this is downwards

Drawing a Born-Haber cycle step 3 - creating the gaseous ions

Drawing a Born-Haber cycle step 4 - completing the cycle

Born-Haber Cycles - Calculations

So, if we rearrange to calculate the lattice energy, the equation becomes

Step 2: Applying Hess’ law, the lattice energy of KCl is:

ΔlattHꝋ = ΔfHꝋ - [(ΔatHꝋ K) + (ΔatHꝋ Cl) + (IE1 K) + (EA1 Cl)]

Step 3: Substitute in the numbers:

Step 2: Applying Hess’ law, the lattice energy of MgO is:

Step 3: Substitute in the numbers:

Polarisation of anion leading to covalent character

4.3.4 Enthalpy of Solution - Key Terms

4.3.5 Enthalpy of Solution - Calculations

ΔsolHꝋ [KCl] = +26 kJ mol-1

ΔhydHꝋ [K+] = -322 kJ mol-1

Step 2: Substitute the values to find ΔhydH[Cl-]

ΔsolH [MgCl2] = -55 kJ mol-1

ΔhydH [Cl-] = -363 kJ mol-1

Step 2: Substitute the values to find ΔHhydꝋ [Mg2+]

Alternative route to find ΔhydHꝋ[Mg2+]

Enthalpy of Solution - Predictions

The expression can become

Therefore the solubility of an ionic solid depends upon three factors

= +113.4 + 146.4 - 151.1

= -86.6 J K-1 mol-1

4.3.6 Enthalpy of Solution - Ionic Charge & Radius

Factors affecting enthalpy of hydration

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